乳状液膜法分离富集中草药中生物碱的研究
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摘要
生物碱是中草药中具有生理活性的一类化合物，具有多种药用价值。目前中草药中生物活性成分分离提取方法主要有液-液萃取、超临界流体提取、超声波提取、微波辅助提取、加速溶剂提取、常温超高压提取、大孔吸附树脂提取和分子印迹提取等。乳状液膜作为一种简单、快速、高效、选择性高、经济节能的新型分离提取技术，已被广泛应用于环境、化工生产、湿法冶金和生物工程等领域。然而由于中草药组成复杂，干扰因素多，使得液膜用于中草药中活性成分的提取的研究报道很少。本论文就乳状液膜法对中草药中生物碱的分离富集进行了较为系统的研究，具体内容如下：
1．综述了近年来常用的中草药中生物碱分离提取技术，重点对乳状液膜法的原理和应用进行了综述。
2．以磷酸二(2-乙基己基)脂(D2EHPA)-司般80(Span 80)-煤油乳状液膜体系对荷叶中阿朴啡类生物碱：N-去甲基荷叶碱·(N-nornuciferine)、O-去甲基荷叶碱(O-nornuciferine)和荷叶碱(nueiferine)进行了提取分离和富集，在优化的实验条件下，对荷叶中三种生物碱Ⅳ_去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的萃取率分别达到了95.6％、100％和97.9％，相应的富集因子依次为：8.73、8.50和8.04。说明该乳状液膜体系能够很好地分离提取荷叶中的这三种生物碱。
3．系统地研究了D2EHPA-Span 80-煤油的乳状液膜体系对小果博落回中异喹啉类生物碱：原鸦片碱(protopine)、别隐品碱(allocryptopine)、血根碱(sanguinarine)、和白屈菜红碱(chelerythrine)的提取分离和富集，在最佳实验条件下，对博落回中四种生物碱原阿片碱、别隐品碱、血根碱和白屈菜红碱的萃取率分别达到了80.4％、77.9％、88.3％和75.6％；四种生物碱的富集因子分别为：8.57、8.31、9.42和8.06。表明该乳状液膜体系能很好地对博落回中四种生物碱进行分离提取。
4．基于绿水化学方面的考虑，我们用无毒的食用茶油代替煤油作为膜溶剂。研究了以D2EHPA-Span 80-n-decanol-食用茶油乳状液膜体系对小果博落回中异喹啉类生物碱：原鸦片碱、别隐品碱、血根碱和白屈菜红碱进行了提取分离和富集，在最佳实验条件下，四种生物碱的萃取率分别为：81.1％、77.8％、98.4％和78.7％；它们的富集因子分别为：10.9、10.5、18.2和16.2。相对于用煤油作为膜溶剂的乳状液膜来说，本体系对生物碱的萃取率略有增大，而富集因子有显著增大：且体系破乳时间大大减少，表明改进的液膜体系具有更好的性能。
Alkaloids in Chinese Traditional Medicine have a variety ofmedicinal value because of their excellent biological activity. Commonseparation methods, liquid-liquid extraction, supercritical fluid extraction,ultrasonic wave extraction, microwave assisted extraction, acceleratedsolvent extraction, common ultra-high pressure extraction, macro-porousadsorption resin extraction and molecular imprinting extraction have beendeveloped to separate and extract bioactive components from ChineseTraditional Medicine. Emulsion liquid membrane, as a simple, quick,high-efficiency, high-selectivity and high-economy separation andextraction technique, has been widely used in the fields of environment,chemistry production, wet metallurgy and biological engineering.However, the reports about separation and extraction of active ingredientsfrom Chinese Traditional Medicine using emulsion liquid membrane arevery few due to the complex composition and multiinterferent exist. Thesystemic study has been carried out in the present paper onseparation andextraction of alkaloids from Chinese Traditional Medicine using emulsionliquid membrane. The details are as follows:
1. A literature review is made on the regular separation and extractionmethods of alkaloids from Chinese Traditional Medicine which appearin recent years, Then, the emulsion liquid membrane is introduced indetail.
2. The separation and extraction of aporphine alkaloids, N-nornuciferine,O-nornuciferine and nuciferine in the lotus leaf have been carried outusing emulsion liquid membrane of D2EHPA-Span 80- kerosene. Under the optimized experimental conditions, the extraction rates ofN-nornuciferine, O-nornuciferine and nuciferine in the lotus leaf reach95.6％, 100％, and 97.9％, respectively. The enrichment factors are8.73, 8.50, and 8.04, respectively. The results indicate that the presentemulsion liquid membrane system can extract and separate effectivelythese three kinds of alkaloids from lotus leaf.
3. A systematic research on the extraction and enrichment of theprotopine, allocryptopine, sanguinarine, and chelerythrine in theMacleaya Cordata (Willd) R. Br. with the emulsion liquid membranesystem of D2EHPA- Span 80- kerosene. Under the optimizedexperimental conditions, the extraction rates of protopine,allocryptopine, sanguinarine and chelerythrine in the macleaya cordata(Willd) R. Br reach 80.4％, 77.9％, 88.3％, and 75.6％, respectively.The enrichment factors of these four alkaloids are 8.57, 8.31, 9.42, and8.06, respectively. The results indicate that the present emulsion liquidmembrane system can extract and separate these four kinds ofalkaloids from the Macleaya cordata (Willd) R. Br. very well.
4. In view of green chemistry, the poisonless edible tea oil was selected asthe membrane solvet instead of kerosene. The research has beencarried out on the extraction and enrichment of the protopine,allocryptopine, sanguinarine, and chelerythrine in the Macleayacordata (Willd) R. Br. with the emulsion liquid membrane system ofD2EHPA-Span 80-n-decanol-edible tea oil. Under the optimizedexperimental conditions, the extraction rates of protopine,allocryptopine, sanguinarine and chelerythrine in the Macleayacordata(Willd) R. Br. reach 81.1％, 77.8％, 98.4％, and 78.7％, respectively. The enrichment factors of these four alkaloids are 10.9,10.5, 18.2, and 16.2, respectively. Comparing the system usingkerosene as the membrane solvent, the extraction rates and theenrichment factors of alkaloids are obvious higher. Moreover, the timeof breaking the milk reduces greatly in the present system. The resultsdemonstrate that the improved membrane system has better function.
1．综述了近年来常用的中草药中生物碱分离提取技术，重点对乳状液膜法的原理和应用进行了综述。
2．以磷酸二(2-乙基己基)脂(D2EHPA)-司般80(Span 80)-煤油乳状液膜体系对荷叶中阿朴啡类生物碱：N-去甲基荷叶碱·(N-nornuciferine)、O-去甲基荷叶碱(O-nornuciferine)和荷叶碱(nueiferine)进行了提取分离和富集，在优化的实验条件下，对荷叶中三种生物碱Ⅳ_去甲基荷叶碱、O-去甲基荷叶碱和荷叶碱的萃取率分别达到了95.6％、100％和97.9％，相应的富集因子依次为：8.73、8.50和8.04。说明该乳状液膜体系能够很好地分离提取荷叶中的这三种生物碱。
3．系统地研究了D2EHPA-Span 80-煤油的乳状液膜体系对小果博落回中异喹啉类生物碱：原鸦片碱(protopine)、别隐品碱(allocryptopine)、血根碱(sanguinarine)、和白屈菜红碱(chelerythrine)的提取分离和富集，在最佳实验条件下，对博落回中四种生物碱原阿片碱、别隐品碱、血根碱和白屈菜红碱的萃取率分别达到了80.4％、77.9％、88.3％和75.6％；四种生物碱的富集因子分别为：8.57、8.31、9.42和8.06。表明该乳状液膜体系能很好地对博落回中四种生物碱进行分离提取。
4．基于绿水化学方面的考虑，我们用无毒的食用茶油代替煤油作为膜溶剂。研究了以D2EHPA-Span 80-n-decanol-食用茶油乳状液膜体系对小果博落回中异喹啉类生物碱：原鸦片碱、别隐品碱、血根碱和白屈菜红碱进行了提取分离和富集，在最佳实验条件下，四种生物碱的萃取率分别为：81.1％、77.8％、98.4％和78.7％；它们的富集因子分别为：10.9、10.5、18.2和16.2。相对于用煤油作为膜溶剂的乳状液膜来说，本体系对生物碱的萃取率略有增大，而富集因子有显著增大：且体系破乳时间大大减少，表明改进的液膜体系具有更好的性能。
Alkaloids in Chinese Traditional Medicine have a variety ofmedicinal value because of their excellent biological activity. Commonseparation methods, liquid-liquid extraction, supercritical fluid extraction,ultrasonic wave extraction, microwave assisted extraction, acceleratedsolvent extraction, common ultra-high pressure extraction, macro-porousadsorption resin extraction and molecular imprinting extraction have beendeveloped to separate and extract bioactive components from ChineseTraditional Medicine. Emulsion liquid membrane, as a simple, quick,high-efficiency, high-selectivity and high-economy separation andextraction technique, has been widely used in the fields of environment,chemistry production, wet metallurgy and biological engineering.However, the reports about separation and extraction of active ingredientsfrom Chinese Traditional Medicine using emulsion liquid membrane arevery few due to the complex composition and multiinterferent exist. Thesystemic study has been carried out in the present paper onseparation andextraction of alkaloids from Chinese Traditional Medicine using emulsionliquid membrane. The details are as follows:
1. A literature review is made on the regular separation and extractionmethods of alkaloids from Chinese Traditional Medicine which appearin recent years, Then, the emulsion liquid membrane is introduced indetail.
2. The separation and extraction of aporphine alkaloids, N-nornuciferine,O-nornuciferine and nuciferine in the lotus leaf have been carried outusing emulsion liquid membrane of D2EHPA-Span 80- kerosene. Under the optimized experimental conditions, the extraction rates ofN-nornuciferine, O-nornuciferine and nuciferine in the lotus leaf reach95.6％, 100％, and 97.9％, respectively. The enrichment factors are8.73, 8.50, and 8.04, respectively. The results indicate that the presentemulsion liquid membrane system can extract and separate effectivelythese three kinds of alkaloids from lotus leaf.
3. A systematic research on the extraction and enrichment of theprotopine, allocryptopine, sanguinarine, and chelerythrine in theMacleaya Cordata (Willd) R. Br. with the emulsion liquid membranesystem of D2EHPA- Span 80- kerosene. Under the optimizedexperimental conditions, the extraction rates of protopine,allocryptopine, sanguinarine and chelerythrine in the macleaya cordata(Willd) R. Br reach 80.4％, 77.9％, 88.3％, and 75.6％, respectively.The enrichment factors of these four alkaloids are 8.57, 8.31, 9.42, and8.06, respectively. The results indicate that the present emulsion liquidmembrane system can extract and separate these four kinds ofalkaloids from the Macleaya cordata (Willd) R. Br. very well.
4. In view of green chemistry, the poisonless edible tea oil was selected asthe membrane solvet instead of kerosene. The research has beencarried out on the extraction and enrichment of the protopine,allocryptopine, sanguinarine, and chelerythrine in the Macleayacordata (Willd) R. Br. with the emulsion liquid membrane system ofD2EHPA-Span 80-n-decanol-edible tea oil. Under the optimizedexperimental conditions, the extraction rates of protopine,allocryptopine, sanguinarine and chelerythrine in the Macleayacordata(Willd) R. Br. reach 81.1％, 77.8％, 98.4％, and 78.7％, respectively. The enrichment factors of these four alkaloids are 10.9,10.5, 18.2, and 16.2, respectively. Comparing the system usingkerosene as the membrane solvent, the extraction rates and theenrichment factors of alkaloids are obvious higher. Moreover, the timeof breaking the milk reduces greatly in the present system. The resultsdemonstrate that the improved membrane system has better function.
引文
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